Friday, February 18, 2011

States

A key concept in thermodynamics is the state of a system. A state consists of all the information needed to completely describe a system at an instant of time. When a system is at equilibrium under a given set of conditions, it is said to be in a definite state. For a given thermodynamic state, many of the system's properties (such as T, p, and ) have a specific value corresponding to that state. The values of these properties are a function of the state of the system. The number of properties that must be specified to describe the state of a given system (the number of degree of freedom) is given by Gibbs phase rule:

f = c - p + 2 ---------- (5a)

where f is the number of degrees of freedom, c is the number of components in the system, and p is the number of phases in the system. Components denote the different kind of species in the system. Phase means a system with uniform chemical composition and physical properties.

For example, the phase rule indicates that a single component system (c = 1) with only one phase (p = 1), such as liquid water, has 2 degrees of freedom (f = 1 - 1 + 2 = 2). For this case the degrees of freedom correspond to temperature and pressure, indicating that the system can exist in equilibrium for any arbitrary combination of temperature and pressure. However, if we allow the formation of a gas phase (then p = 2), there is only 1 degree of freedom. This means that at a given temperature, water in the gas phase will evaporate or condense until the corresponding equilibrium water vapor pressure is reached. It is no longer possible to arbitrarily fix both the temperature and the pressure, since the system will tend to move toward the equilibrium vapor pressure. For a single component with three phases (p = 3 -- gas, liquid, and solid) there are no degrees of freedom. Such a system is only possible at the temperature and pressure corresponding to the Triple point.

One of the main goals of Thermodynamics is to understand these relationships between the various state properties of a system. Equations of state are examples of some of these relationships. The ideal gas law: